Process for breaking petroleum emulsions



Patented'Nov. 11, 1941 PROCESS FOR BREAKING PETROLEUMI EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves,

Mo., as'signors to Petrolite Corporation, Ltd, Wilmington, Del., a

corporation of Delaware No Drawing. Application June 27, 1940, Serial No. 342,724

- ways: The high molecular weight carboxy acid,

9 Claims.

This invention relates primarily to the resolution oi petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

.The composition of matter which we prefer to use as the demuls'ifler of our process, can be produced by reacting a polybasic carboxy acid compound containing at least one high molecular weight carboxy acid radical, with a polyamine of the following types:

alkyl, RCO, RC0.0X, and RC0.0X'., in which RC is an acyl radical derived from a lower molecular weight carboxy acid having six carbon atoms or less; RCODX is a radical in which OX represents a divalent radical obtained at least hypothetically by the removal of a hydroxyl hycomposition of matter has unusual effectiveness as a demulsifier, and is intended to be used as the treating agent in practising the process which constitutes another feature of our invention.

Such high molecular weight carboxy acid can be united with a polybasic acid in two general usually a monocarboxy acid, may contain an alcoholic hydroxyl group as part of the acyl radical. For instance, ricinoleic acid, hydroxystearic acid, and the like serve to illustrate this particular type. In other instances, the high molar car- .boxy acid may be combined with a polyhydric alfor the manufacture of the compounds of the kind herein contemplated is to combine a polybasic carboxy acid, and particularly, a dibasic acid, such as phthalic acid or anhydride with the selected hydroxylated high molecular weight carboxy acid body, in such a manner as to obtain a material which has at least one free carboxyl radical-in other words, in essence, a fractional ester. Such fractional'ester can then be combined with a hydroxylated alkylene diamine of the kind hereinafter described, to produce an acylation product, i. e., a product which involves either ester linkages or amide linkages, or both. The expression fractional ester is employed in the hereto appended claims to indicate a compound containlnggat least one free carboxyl radical, attached to a polybasic acid nucleus, and which may or may" not contain one or more hydroxyl radicals.

The expression higher molecular weight carboxy acids" is an expression frequently employed to refer to certain organic acids, particularly monocarboxy acids, having more than 6 carbon atoms and generally less than 40 carbon atoms. The commonest examples include the. detergentforming acids, i. e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturallyeoccurring fatty acids, resin acids, such as abietic acid, naturally-occurring petroleum acids, such as naphthenic acids,'and carboxy acids produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids wl ich have somewhat similar characteristics and are derived from somewhat difierent ,sources and are different in structure, but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, including caprylic acid, butyric acid, h'eptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated and unsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at least 8 carbon atoms, and including, in addition to those mentioned, melissic acid, stearlc acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid, ricinostearolic acid, ricinoleyl lactic acid, acetylricinoleic acid, chloracetyl-ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, undecylenic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor'oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as those mentioned: hydroxy and aipha-hydroxy higher carboxylic, aliphatic and fatty acids, such as dihydroxystearic acid, dihydroxy palmitic acid, dihydroxybehenic acid, alphahydroxy capric acid, alphahydroxy-stearic acid, alphahydroxy palmitic acid, alphahydroxylauric acid, alphahydroxy myrlstic acid, alphahydroxy cocoanut oil mixed fatty acids, alphahydroxymargaric acid, alphahydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes, such as beeswax, spermaceti, montan wax, japan wax, coccerin, and camauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. As'suggested, one may 'also employ higher molecular weight carboxylic acids derived, by oxidation and other methods, from paramn wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogen- 'of the following general formulas:

where a: is a whole number; or they may be ring I poundshaving the general formula:

(051':i i,NH),.c,m.NH-

where a: is a whole number. The first group is exemplified by diethylene triamine,

(NHa.C2H4.NH.CaH4.NH2) triethylene tetramine,

(NmcmmHcamNHcn-nm) and tetraethylene pentamine,

(N'Igh.CzHaNHCaHaNHCaHLNHCQHi-NHZ) ascasss Examples of the second group are diethylene diamine.

and triethylene triamine:

CIHI CIHI NHCsHiNH In the above formulas the radical C2114 is simply a divalent linking radical. Thus, preceding formulas may be rewritten as follows:

in which T represents any suitable divalent linking radical. If T is an oxygenated divalent linking radical of the kind to be described, and if such polyamines are acylated so as to introduce an acyl radical from a higher molecular weight carboxy acid of the kind previously defined, one obtains a new composition of matter and a compound or a variety of compounds which are particularly effective as demulsiflers for water-inoil emulsions.

Generally speaking the oxygenated divalent linking radical is exemplified by three types: the keto type, in which the conventional carbonyl linkage appears; the ether type, in which the conventional ether linkage appears and the hydroxylated type, in which the conventional alcoholic hydroxyl radical appears. One of the best known examples are compounds obtained from fip'-dichloralkyl ethers, instead of alkylene dichlorides. Such compounds are characterized by the preceding formulas if one adds the proviso that in such formulas T shall represent the divalent radical CHzCHzOCHzCI-Ia. As to the manufacture of such compounds, see U. 8. Patent No. 1,919,301, dated July 25, 1933 to Morton. Said patent is concerned largely with compounds containing an aryl radical: but of course, the same procedure is equally eifective in connection with ammoniaor amines free from an aryl radical and containing at least one reactive hydrogen atom; i. e., the selected amines must be primary or secondary. Furthermore, one is not limited to,

the ethyl ether halogen derivative; but one may use the propyl ether halogen derivative or any other suitable compound. If derived from ammonia, such diamines may be alkylated in the .nary amines, i. e., monoamines. Alkylation may result in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated diamines are most readily obtainable. For instance, alkylated products may be derived by reaction between alkyl chlorides, such as aacasss propyl chloride, butyl chloride, amyl' chloride, cetyl chloride, and the like. Such reaction products result in the formation of hydrochloric acid, and the resultant product consists of an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group; but as a matter of fact, a radical may be introduced characterized by the fact that the carbon atom chain is interrupted at least once by an oxygen atom. In other words, alkylation may be accomplished by compounds which are essentially alkyloxyalkyl chlorides, as, for example, the following:

CHsOCnHsCl CzHsOCaHsCl CzHsOCaHxCT CaHmOCeHrsCl As a matter of common knowledge, reactions involving ammonia and an alkyl ether dichloride probably go through an intermediate stage which involves the formation 01 aminoalkyl ether halide. As a result; one has another suitable procedure for manufacture of the diamines, i. e., a reaction involving amino alkyl ether halides and a monoamine. See British Patent No. 292,615, to I. G. Farbenindustrie A.-G., application date in the United Kingdom June 22, 1928.

As has been previously stated, the reaction involving the alkyl ether dichlorides is not limited to ammonia, but may involve amines, such as. ethylamine, propylamine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Similarly, the reaction may involve the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds may be derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two difierent amines.

It is known that there are numerous other I compounds which are akin to the dichloralkyl ethers, in that they are labile or reactive alphaomega-dichloro derivatives. Thus, well known reactants which supply a-divalent linking radical of the kind indicated by T in previous formulas include: dichlorodiethyl ether (ClCzHsOCzI-IaCl); chloroethoxy triglycol dichloride; tetraglycol dichloride; dichlorodi-isopropyl e t h e r (ClCaHvOCsHvCl) dichlorodiisobutyl e t h e r (C1C4H9OC4H9C1) glycerol dichlorhydrin; methyl glycerol dichlorhydrin; polyglycerol dichlorhydrins; dichloracetone o (ClCHr--CHaCl) derived from acetone; dichlormethylpropyl ketone omci Garcons omen etc.

Various other procedures may be employed for producing polyamines of the kind described. For instance, reference is made to our co-pending application for patent Serial No. 273,278, filed May 12, 1939. In said application there is described the conversion of triethanolamine into an alcoholate, such as monoalcoholate, by means of caustic soda and the like, and subsequently uniting two moles of such compound by means similarly, the dialcoholate might be treated in the same manner. Incidentally, such alcoholates may be derived from hydroxyalkyl ethers of tertiaryamines,,as well as materials of the kind dated August 22, 1933.

Other suitable procedure involves hydroxyamines, such as-diethanolamine, an aldehyde,

of a material such as' glycerol dichlorhydrin.

particularly formaldehyde, and a ketone or poly. ketone having present alpha-hydrogen atoms.

As to such general reactions, see U. 3. Patent No. 1,071,007, to Merling, dated August 19, 1913.

In the manufacture of certain diaminesand their obvious modifications, which can be made in many instances to yield higher polyamines, i. e.. analogous or comparable products having at least three amino nitrogen atoms, generally speaking, if the amine or ii ammonia is treated with a reactant having a divalent linking radical and two labile halogen atoms, such as chlorine atoms, one is apt to obtain varying amounts of such higher polyamines. For the sake of brevity, further indications will be limited to procedures for making various suitable polyamines. Such suitable polyamines will be the following:

CHz-CHr-N I CHr-CHr-OH I (A) CHI-CHI-OH CHr-C Hr-N NH- C Hr-CH-CHB H-OH Hz 0H NH-C Hr- H-CHI (See German Patent No. 635,904, to I. G. Farbanindustrie, A.-G., dated October 1, 1906).

N,N'-di(2-hydroxy-3-amino propyD-2-hydroxy propylene diami'ne-LS.

)U. 8. Patent 2,046,720, to Bottoms, dated July See also U. s. Patent No. 2,132 014, to Kartaachoi! and Aeschlimann, dated October 4, 1938.

Among products commercially available is 1,3- diamino-Z-propanol, which is an especially suitable reactant.

It has been pointed out that polyamines oi the kind previously described may be produced glycol, etc.

or reacted in such a manner that the amino hydrogen atom is replaced by an alkyl radical, a hydroxyalkyl radical, a hydroxyalkyloxyalkyl radical, or the like. It is well known that certain other modifications can be obtained by conventional procedure. For instance, one may introduce acyl radicals derived from acids having 6 carbon atoms or less, such as acetic acid, butyric acid, and the like. Such products are obtained by treatment with acetic anhydride, acetyl chloride, or equivalent reactants. Furthermore, it is known that one can obtainderivatives of amines of the kind described by reactions with chlorhydrins derived from polyglycols, polyglycerols and the like, such as diglycerol chlorhydrin, the chlorhydrin derived from the dihydric alcohol obtained by etherizing two moles of diethylene Similarly, amino hydrogens may be substituted by reaction with compounds of the kind typified by ethyl chloracetate, i. e., esters of carboxy acids. in which an alpha-hydrogen has been substituted by chlorine. been suggested previously, amino alkyl chlorides =may be employed so as to introduce an amino alkyl group. As an example of such amino alkyl halide, reference is made to the description of certain examples found in U. S. Patent No.

2,014,077, datedSeptember 10, 1935, to Wilson. Furthermore, in certain instances polyamines suchas diamines may be employed. Certain other compounds may be looked upon as instances in which one of the amino hydrogen atoms of a polyamine, particularly a diamine, has been replaced by an amino alkyl group. For the sake I of brevity, in the hereto appended claims the expression alkyloxyalky is intended to in clude the type of oxyhydrocarbon radical where Similarly, as has ..cedure for acylating diamines, including hydroxylated diamines, is well known. In the present instance, as a variation, one employs a suitablepolybasic acid or any functional equivalent. For convenience, amines of the above type which can be acylated, i. e., have present a reactive hydrogen atom, will be referred to as acylationre'active amines. Such acylation products may be of the'amide type, in other words, of a type inwhich the acyl group is directly attached to the amino nitrogen atom; or they may be of the ether type, where the acyl group replaces a hydroxyl hydrogen atom, and thus is linked to a nitrogen atom through a carbon chain; or the acylation derivative may exemplify both types where the amine employed as a raw material has present at least one aminohydrogen atomand at least one hydroxyl hydrogen atom. As has been previously stated, it is unnecessary to describe to any length the method of producing the acylation products, except to indicate that the same means may be employed as in connection with the acylation of any ordinary amine, whether a monoamine or a diamine, although the employment of a polybasic compound may be considered as a variation.

matter herein contemplated, and particularly, for

It is understood, that the new composition of use as a demulsifier, may be prepared in any suitable manner.

' of 'manufacture is specifically recited. As has the hydrocarbon chain is interrupted more than once by an oxygen atom. Similarly, since materials such as ethyl chloracetate are sometimes spoken of as alkylating agents; it is intended that the expression alkyl will include the type of radical so introduced, 1. e., a radical exemplifled by the following: CH2COOC2H5, although strictly speaking, it is not, of course, an alkyl radical.

Summarizing what has been said thus far, it is apparent that one could readily obtain amines of the following type:

in which a: is a small whole number less than 10 but including zero, T has its previous significance and D may be hydrogen, alkyl, alkylol, hydroxyof a hydroxyl hydrogen atom from an alkylol radical; and RCQOX' denotes a radical in which OX represents a radical derived, at least hyp0 thetically, by the removal of a hydroxyl hydrogen atom from a hydmxyalkyloxyalkyl radical. If one adds the proviso that there must be a reactive hydrogen atom present in such polyamine,

i. e., a hydrogen atom linked to a nitrogen atom or to an oxygen atom, one then has an acylationreactive polyamine.

In other words, such polyamine can be acylated so as to introduce a polybasic carboxy acid acyl group in the same manner that any other amine can be acylated, i. e., an. ordinary monoamine or been stated, it is our preference to obtain an acylation-reactive amine of the type or kind just described, and react the same with a polybasic carboxy acid compound or its functional equivalent. It is our preference to use thetype of polybasic acid compound which is characterized by the presence of an acyl radical of the detergentforming acid type, which includes fatty acids, resin acids, and petroleum acids. Such petroleum acids may be naturally-occurring acids, such as naphthenic acid, or may be obtained by the oxidation of parafilnor-the like. or the various detergent-forming acids which may be employed to supply the detergent acid type acyl radical, we prefer to use fatty acids, and most particularly, hydroxylated fatty acids, such as ricinoleic acid.

Previous reference has been made to the introduction of an aminoalkyl radical in place of an amino hydrogen atom. The availability of a compound of the following types:

would permit the introduction of a hydroxyalkylamino radical. However, the introduction of such type radical is more feasible by introducing an aminoalkyl radical from a compoundv such as, for instance, chloramylamine such as ethylene oxide, or any similar a c alkylene oxide or with glycid, epichlorhydrin and other reagents, so as to convert one or both of the amino hydrogen atoms in the above described aminoalkyl radical into a hydroxyalkyl radical, or, in the case of ethylene oxide, into a C2H4OH radical. Needless to say, such a radical, which is in essence an alkylolamine radical or an alkylolamine residue, can be acylated by acids of low molecular weight, in the same manner that has been described previously in regard to any alcoholic hydroxyl which happens to be present.

Summarizing what has been said, it is obvious that the polyamine of the kind described can be characterized by the following formulas:'

in which a: is a small Whole number including 0, but in any event,less than 10, and preferably 1 to 4 T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D may be hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCOOX, RCOOX', RCOOX", RCOOX; RC is an acyl radical. derived from a lower molecular weight carboxy acid having 6 carbon atoms or less; OX represents a divalent radical obtained at least hypothetically by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived at least hypothetically by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived at least hypothetically by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived at least hypothetically by removal of a hydrogen atom from a hydroxyalkylamino radical.

Attention is directed to the fact that the word "amidification has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical, without conventional limitation to a reaction involving ammonia. The replacement of the amino hydrogen atom of a primary amine or a secondary amine by an acyl radical has been considered as being amidificavtion, rather than the formation of a substituted amide, or the formation of an imideor substituted imide. Such obvious departure from conventional nomenclatures has been for purposes of simplicity and to show the similarity between certain reactions.

It is to be understood that the compound herein contemplated may be manufactured in any suitable manner; and one is not dependent upon following the exact procedure previously outlined. In certain instances the other reactants might be employed, or else reactants of the kind previously described might be combined in some other manner. It is not intended that the hereto appended claims be limited in any manner whatsoever as to the method of manufacture, unless such method is specifically recited.

The polybasic acids which may be employed, including some having at least three carboxyl radicals, are phthalic, succinic, malic, fumaric, citric, maleic, adipic, tartaric, glutaric, diphenic, naphthalic, oxalic, tricarballylic, etc. Instead of the acids themselves; one may use any suitable functional equivalent, and particularly, the anhydrides. We prefer to use oxalic acid, maleic acid, and phthalic acid. In the use of maleic acid and phthalic acid, we particularly prefer to use the anhydrlde, l. e., maleic anhydride and phthalic anhydride. It is understood that in the hereto attached claims any references to the acid or the anhydride is intended to be interchangeable.

The manufacture of fractional esters, characterized by having present: (a) a detergent-forming acid radical; and (b) a free carboxyl radical directly attached to a polybasic acid residue, is well known. Such materials have found utility in various arts. The same procedure which is employed inconnection with the detergent-forming acids would apply to any of the high molecular weight carboxy acids previously described, and particularly, those which are primarily monocarboxy in nature.

Likewise, the procedure followed in respect to the detergent-forming acids is best exemplified by the fatty acids, although obviously, the same procedure is equally suitable for resin acids and petroleum acids, whether naturally-occurring or obtained by the oxidation of paraffin or the like.

In order to eliminate lengthy detailed description of these particular materials, which are well known compositions of matter, reference is made to U. S. Patent No. 2,166,431, dated July 18, 1939, to Melvin De Groote, and particularly, to the subject-matter which appears on page 4, right hand column, lines 36, through page 5, right hand column, line 16; and also to U. S. Patent No. 2,166,433, dated July 18, 1939, to Melvin De Groote, beginning on page 4, right hand column, line 39, through page 6, right hand column, line 62.

In subsequent examples reference will be made to the manufacture of our new composition of matter by reacting a polybasic acid derivative of a detergent-forming acid compound, or, for that matter, a derivative of any high molecular weight carboxy acid, with a hydroxylated polyalkylene diamine of the kind previously described. It is understood, however, that the composition of matter could be obtained in any suitable manner, and that in the hereto attached claims it is not intended that there shall be any limitation as to the procedure employed. For instance, one might first combine the selected amine with a polybasic carboxy acid by means of an acylation reaction in such a manner as to have present a free carboxyl radical attached to the polybasic carboxy acid. Such product then might be esterified with cals derived from polybasic carboxy acids and not united to the amine residue. For instance, diphthalated castor oil could be reacted with the selected amine in such a manner that only one phthalic acid radical is united with the amine.

The other phthalic acid radical may remain in the acidic state, or the carboxy hydrogen atom could be replaced in any suitable manner, as described. Furthermore, if a tribasic acid is employed, such as citric acid, then two carboxy radicals might be employed to unite the carboxy detergent-forming residue or the like with the I amine residue, and the remaining carboxy radiresidue. In other words, one is not limited to,the

use of a polybasic carboxy acid; but one might employ some suitable form in which one carboxylic hydrogen atom had already been replaced in a manner above described. For instance, one might use sodium hydrogen phthalate, potassium hydrogen phthalate, sodium hydrogen maleate, potassium hydrogen maleate, octyl hydrogen phthalate, cetyl hydrogen maleate, ethyl hydrogen phthalate, or the like, in place of the polybasic carboxy acids themselves. Polybasic acids having more than two carboxyls may have two such substituents, such as disodium citrate.

Similarly, the acidic material containing a free carboxyl radical may be neutralized with a suitable base, esterified with a suitable alcohol, particularly, an aliphatic alcohol, such as ethyl, methyl, propyl, butyl, or octyl alcohol; or one may eliminate the acidic hydrogen carboxyl if present by an amine, so as to form a substituted ammoniumsalt; or if the amine is hydroxylated, as in the case of triethanolamine, one may form an ester in which the amine supplies the alkyl radical. However, where only one mol of a dibasic acid is employed for each mol of higher molal carboxy acid, then both carboxyl radicals are involved in the reactions, without a residual carboxyl hydrogen atom being present.

In thepreferred type of material, we employ a compound, in which, as has been previously indicated, a carboxyl group of the polybasic carboxy acid has been caused to unite with a hydroxylated detergent-forming acid body. As has been previously noted, the detergent acids include fatty acids, particularly the higher fatty acids, resin acids, petroleum acids, such as naturallyoccurring petroleum acids, and also petroleum acids obtained by the oxidation of paraflin hydrocarbons or the like. For the sake of brevity,

One mole of phthalic anhydride may be esterified with a mole of ricinoleic acid, diricinoleic acid, polyricinoleic acid, chlororicinoleic acid, or the like. Similarly, one might employ an ester, such as ethyl ricinoleate, propyl ricinoleate, butyl ricinoleate, octyl ricinoleate, benzyl ricinoleate, cyclohexyl ricinoleate, etc.

Another procedure would be to employ one or two moles of the phthalic anhydride and the ester of a dihydric alcohol, such as ethylene glycol diricinolein, propylene glycol diricinolein, etc. Similar derivatives may be obtained from hydroxystearic acid or polyhydroxylated stearic acids of the kind described in U. S. Patent No. 1,835,203, dated December 2, 1931, to Bruson. Similarly, one may employ the esters of glycerine, such as triricinolein, trihydroXystearin, etc.

Instead of depending on the hydroxyl group as being part of the acyl radical, one may, as previously suggested, employ compounds in which the hydroxyl radical is part of the polyhydric alcohol residue. Thus, one might employ monostearin, mono-olein, mononaphthenin, monoreference will be made to phthalic anhydride.

abietin, or similar compounds obtained from oxidized petroleum acids. One can also employ the type of materials in which there are two acyl groups attached to the polyhydric alcohol residues, for instance, distearin, di-olein, dinaphthenin, etc. Similar hydroxylated compounds can be derived from the various glycols, from materials such as sorbitol, mannitol, sorbitan, mannitan, pentaeryrithritol, diglycerol, polyglycerol, diglycols, etc. obtain materials of the kind in which there is at least one hydroxyl radical present as part of the acyl group, and at least, one hydroxyl radical present as part of the polyhydric alcohol residue, as, for example, monoricinolein, diricinolein, monohydroxystearin, dihydroxystearin, the ricinolein mono-ester of ethylene glycol, or similar glycols, etc.

The following are examples of the new composition of matter that constitutes one feature of our present invention, and which is adapted to be used as a demulsifier in practising our process for resolving petroleum emulsions:

Composition of matter, Example 1 An amine of the following type:

previously described is acylated with a molar proportion of triricinolein monophthalate. The product so obtained is entirely of the amide type.

Composition of matter, Example 2 The same procedure is followed as in the preceding example, except that an amine of the following type is employed:

\ oruon) CHI CH1 NH: I 15H;

is employedfollowing the same procedure as in Composition of matter, Example-.1. The acylated product so obtained is entirely of the ester type.

Composition of matter, Example 4 An amine of the following type:

NH-CHz-C H-CHa I I NH-CHz-CH-C H:

is employed, and one employs the same procedure as in Composition of matter, Example 1.

triglycerol, Similarly, one may Composition of matter, Example The same procedure is employed as in Composition of matter, Example 1, except that one employs either one of the following two amines or a mixture thereof: N-(2-hydroxy-3-aminopropyl) Z-hydroxy propylene diamine-1,3; N,N-di(2-hydroxy-B-arnino propyl)-2-hydroxy propylene diamine-1,3.

Composition of matter, Example 6 1,3-diaminp-2-propanol is acylated with triricinolein monophthalate.

Composition of matter, Example 7 In all the preceding examples there are at least two and usually more than 2 reactive hydrogen atoms. Thus, the procedure of the preceding 6 examples is repeated by employing two moles of monophthalated triricinolein for each mole of amine.

Composition of matter, Example 8 The same procedure is employed as in the preceding 7 examples, except that triricinolein diphthalate is employed.

Composition of matter, Example 9 The same procedure is followed as in the previous examples, except that mono-olein monophthalate is employed in place of triricinolein monophthalate.

Composition of matter, Example 10 The same procedure is followed as in c0ii1, position of matter, Example 8, preceding, except that mono-olein diphthalate is substituted for triricinolein diphthalate.

Composition of matter, Example 11 Composition of matter, Example 12 One follows the preceding example, except that the analogous maleated product derived from maleic anhydride instead of phthalic anhydride is employed.

An examination of what has been said pre viously in regard to the manufacture of the composition of matter herein contemplated, reveals the fact that the diamines of the type described invariably contain at least one reactive hydrogen atom, and may contain more than one, and in fact, usually do contain more than one.

Reactive hydrogen atoms, of course, refer to such hydrogen atoms, directly linked to nitrogen or oxygen; i. e., to hydroxyl hydrogen atoms, or amino hydrogen atoms. The acyl group derived from a polybasic carboxy acid may be introduced in either position, i. e., as a substituent for either or both types of reactive hydrogen atoms. When such group enters an amino hydrogen atom, it forms an amide. When it enters a hydroxyl hydrogen atom position, it forms an ester. Under vigorous conditions of amidification one might obtain secondary amides. One can readily obtain the types in which there is both the amide linkage and the ester linkage. If desired, one may have present an acyl group like.

derived from a lower molecular weight acid, i. e., one having 6 carbon atoms or less; for instance, acetic acid, propionic acid, butyric acid, or the The presence of such acyl radical is not intended to represent anything more than the equivalent of the presence of an alkyl radical.

In general, all the acylation reactions of the kind described take place readily by reactions involving the selected materials in such a manner that any water which is formed is eliminated. Acylation can be accompanied by the elimination of ether compound, such as NI-Ia or 1101. Usually, this means employment of a temperatur above C. and below the point of decomposition. Generally, a temperature of -180" C. is most suitable. A dry, inert gas may be passed through the mass during reaction to hasten acylation. It is understood, of course, that such acylation reactions do not include salt formation. In other words, if the intermediate raw material is of the basic type, it can form a salt with an acid such as citric acid or phthalic acid. On heating such salt, acylation products are obtained.

Since at times there is some confusion as to the use of the word acyl or the like in connection with polybasic acids, insofar that there is more than one carboxy hydroxyl group present, it is deemed desirable specifically to point out that the word acyl or its equivalent is used in the present instance to mean the removal of one or more carboxy hydroxyl groups, without limitation as to the nature of any carboxyl groups that may remain, i. e., without limitation as to being in the acidic state or neutralized state. This may be illustrated in the following manner:

If a polybasic acid be indicated by the following formula:

(COOH)...

in which D represents a polybasic acid residue, in and n represents small whole numbers, including zero, and usually not over three, with the proviso that m plus it must be at least 2, and Z represents any metal, ammonium radical, substituted ammonium radical, or monovalent or-- ganic radical which replaces a carboxylic hydrogen, then examples of acyl radicals derived from such polybasic carboxy acids include the following types:

COOH COOZ CO CO COOH COOZ D-COOH DCOOZ CO CO COOH COOZ D -CO D-CO CO CO CO COOZ D-{CO DCOOH CO CO Th word phthalyl will be given the corresponding breadth of definition.

In such instances where the amine contains at least two hydroxyl radicals, or at least two amino hydrogen atoms, or at least one hydroxyl radical and at least one amino hydrogen atom,

' resinous typeof material.

reactions involving glycerol or glycol or mono-z manner as phthalic anhydride.

raw material.

. less expensive raw material;

It is to be noted that the'express'ion alkyloxyalkyl is used in the hereto appended claims to indicate .a radical in which the carbon atom then one is dealing with a polyfunctional or'bi-' I I functional compound; and thus reactions involving such types ofcompounds with a polybasic acid or dibasic acid, such as phthalic'an hydride, will produce a sub-resinous or semi- Compare analogous ethanolamine with dibasic or polybasic acids.

- However, diphthalated. triricinolein, as any similar polycarboxy derivative will act in the same Our preferred obtained. at least hypothetically by removal-of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived at least hypothetically by-removal ofa hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical;

I OX" represents a divalent radical derived at I least'hypothetically. by the removalof an amino reagent is derived froman amine which is polyfunctional and is most desirably of th subresinous, type, although it may be a monomer, dimer, or 'trimer.

reaction is completed and is'soluble' in one or more solvents which .may be hydrophobe or hydrophile in nature, includingsolutions of such acids as acetic acid, hydrochloric acid, 1 etc. Polymers may represent repeated monomers with eliminationof water or the like. I

' Certain obvious functional equivalents suggest themselves and need not be described in detail.

For instance, a vhalogenated ricinoleic acid. body might be employed just as advantageously as anordinary ricinoleic acid body. 'No advantage I would be obtained by the use of more expensive Similarly, chlorinated 'phthalic. I

anhydride or acid might be used in place of the In other words, itis -prefer-. ably a compound or a mixture of compounds .which still represents a liquid or plastic or fusible: mass at, a temperature in'which the final alkyl is .intendedat .all times, particularly-in the claims, to include products of the kind de-' rived from ethyl chloracetate or the like; and

- the expression .alkyloxyalkyl is intended similarly to includev products; in which the carbon atom chain is interrupted more than once by oxygen; This last statement is intended par-. ticularly to apply inre'spect to the hereto at-' I tached claims. I In thehereto ap'pendedclaims, reference to a high molecular weight-carbox-y'acidresidue;

a detergent-forming acid residue; a fatty acid residue/ or .a ricinoleic acid residue are intended to refer'to the residue or radical derived I not only from the .fatty acid, but also from an 'ester by dehydro'xylation- In other words, it is chain is interrupted at least once byoxygen and. I

might be interrupted more than once, for instance, if derived 'fromacompound obtained by the etherification of two moles ofdiethylene glycol.

. In the hereto appended claims, the expression alkylol is not intended to be limited to monohydroxy alkyl radicals, but is intended to include polyhydroxylated alkyl, radicals.

It is to be noted that some of the compounds described are basic in-character, due to the presence of an unacylated basic amino nitrogen atom, or due to the presence of an esterified group of the kind described. In such instances the compound may be employed as such, or may be employed in basic form (1. e., after combination with water), or may be employed in salt form by reaction with an acid, such as acetic acid, lactic acid, hydrochloric acid, or any other suitable acid,

Summarizing, then, what has been said, it will be appreciated that the present composition of matter may be characterized as acylated derivatives of a polyamine of the kind which can be characterized by the following formulas:

in which a: is a small whole number including 0, but in any event less than 10, and preferably 1 to 4; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D may be hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RC0.0X', RCOQX", and RC0.0X"; in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having 6 carbon atoms or less; OX represents a divalent radical not limited to a residue obtained by dehydrox-ylation of hydroxy naphthenic acid, hydroxy abietic acid, or ricinoleic-acid, but is intended toinclude residues obtained by 'deh'ydroxylation .of' the esters, such as the dehydroxylation of triricinolein, monostearim; distearin, .rnono'naph- I thenin, dinaphthenin, monoabi'etimdiabietin, and

similar esters derived from the glycols and characterized bythe-presence of an alcoholic hydroxyl as part of the polyh ydric'alcohol radical. I I I Conventional demulsifying agents employed 1 the treatment of oil field emulsions are used as such, or after dilution with'any suitable solvent,

such as water-petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous 501- vents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixedv with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable well known classes of demulsifying agents. I

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to -l0,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

It is to. be noted that some of the compounds described are basic in character, due to the presence of an unacylated basic amino nitrogen atom, or due to the presence of an esterified group of the kind described. In such instances the compound may be employed as such, or may be employed in basic form (1. e., after combination with water), or may be employed in salt form by reaction with an acid such as acetic acid, lactic acid, hydrochloric acid, or any other suitable .are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RC0.0X, RC0.0X, and RC0.0X'; in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl presence of:

This particular type radical; OX represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and 021" represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said 'acylation product being characterized by at least one residue derived from a fractional ester, which fractional ester in turn is characterized by the (a) at least one high. molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a high molecular weight carboxy acid residue.

. 2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a sub-resinous demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than 10; T. is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RCODX, RC0.0X", and RC0.0X; in which RC0 is an acyl radical derived from a lower motional ester in turn is characterized by the pres-' ence of: (a) at least one high molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a high molecular weight carboxy acid residue.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a sub-resinousdemulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than 10; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the other type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RC0.0X', RC0.0X", and RC0.0X; in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said acylation product being characterized by at least one residue derived from a fractional ester, which fractional ester in turn is characterized by the presence of: (a) at least one high molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a detergenteforming monocarboxy acid residue.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a sub-resinous demulsiiier comprising an acylation derivative of a, -polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than 10; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl,

Y aminoalkyl, hydroxyalkylamino, RCO, RC0.0X,

RCQOX, RC0.0X", and RC0.0X"; in which RC is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said acylation product being characterized by at least one residue derived from a fractional ester in turn is characterized by thepresence of: (a) at least one high molecular weight carbox'y acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a higher fatty acid residue derived from a fatty acid having more than 8 and not over 22 carbon atoms.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a subresinous demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than 'I is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl; alkylol, hydroxyalkyloxyallcyl, aminoalkyl, hydroxyalkylamino, RCO, RCODX, RCQOX', RCOOX", and R000 in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxvalkyl radical; 0 represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said acylation product being characterized by at least one residue derived from a fractional ester, which fractional ester in turn is characterized by the presence of: (a) at least one high molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a higher unsaturated fatty acid residue derived from a fatty acid having more than 8 and not over 22 carbon atoms. I

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a sub-resinous demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

in which a: is a small whole number including 0, but in any event less than 10; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCOOX, RCOOX, RCODX", and RC0.0 in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said acylation product being characterized by at least one residue derived from a fractional ester, which fractional ester in turn is characterized by the pres- -ence of: (a) at least one high molecular weight\ carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there is at least one polybasic carboxv acid radical acting as a linking radical between the amine residue and a ricinoleic acid residue.

'7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a subresinous demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

but in any event less than 10; T is an oxyhydrocarbon radical of the keto type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, .hydroxyalkylamino, RCO, RC0.0X, RCODX, RCOOX", and RC0.0X; in which RC is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen' atom from a hydroxyalliyloxyalkyl radical; OX represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX represents a radical derived by removal of a hydrogen atom from a hyof the Water-in-oil type, characterized by sub-,

jecting the emulsion to the action of a subresinous demulsifler comprising an acylation derivative of a polyamine selected from the class consisting of the following formula types:

NDg.T.(T.ND),.N Dg

in which a: is a small Whole number including 0,

but in any event loss than 10; T is an oxyhydrocarbon radical of the ether type; and D is selected from the class consisting of hydrogen, alkyl, alkylol,- hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCODX, RC0.0X', RC0.0X", and RC0.0X"'; in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a droxyalkylamino radical; said acylation prodnot being characterized by at least one residue a derived from a fractional ester, which fractional ester in turn is characterized by the presence of: (a) at least one high molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation hydroxy-alkyloxy'alkyl radical; OX" represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived r by removal of a hydrogen atom from a hyderivative being additionally characterized by the fact that there is at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a ricinoleic acid residue.

9. A process for breaking petroleum emulsions of they water-in-oil type, characterized by subjecting the emulsion to the action of a subresinous demulsifier comprising an acylation derivative of a polyamine selected from the class consisting of the following formula type:

in which a: is a small whole number including 0, but in any event less than 10; T is an oxyhydrocarbon radical of the alcohol type; and D is 4 selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RC0.0X', RC0.0X", and RC0.0X'; in which RC0 is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived by removal of an amino hydrogen atom from an aminoalkyl radical; and OX represents a radical derived by removal of a hydrogen atom from a hydroxyalkylamino radical; said acylation product being characterized by at least one residue derived from a fractional ester, which fractional ester in turn is characterized by the presence of: (a) at least one high molecular weight carboxy acid radical; and (b) at least one polybasic carboxy acid radical; and said acylation derivative being additionally characterized by the fact that there isv at least one polybasic carboxy acid radical acting as a linking radical between the amine residue and a ricinoleic acid residue.

MELVIN DE GROOTE.

BERNi-IARD KEISER. 

